CN100339172C - Method for spheroidizing and pelletizing to coagulate metal powder, metal powder and electrolytic capacitor anode - Google Patents
Method for spheroidizing and pelletizing to coagulate metal powder, metal powder and electrolytic capacitor anode Download PDFInfo
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- CN100339172C CN100339172C CNB2006100909132A CN200610090913A CN100339172C CN 100339172 C CN100339172 C CN 100339172C CN B2006100909132 A CNB2006100909132 A CN B2006100909132A CN 200610090913 A CN200610090913 A CN 200610090913A CN 100339172 C CN100339172 C CN 100339172C
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Abstract
The metal powder spheroidizing and pelletizing process includes the following steps: 1. crushing metal powder to average diameter D50 smaller than 50 microns; 2. adding volatile liquid and pelletizing the mixture into wet pellet; 3. stoving to form flowable pre-agglomerated pellet with increased density and volatile liquid eliminated; 4. heat treatment; and 5. sieving to obtain flowable agglomerated metal powder.
Description
Technical field
The present invention relates to the method for nodularization granulation cohesion metal dust and the metal dust made from this method and with the electrolytic capacitor anode of this powder manufacturing.Be particularly related to the method for nodularization granulation cohesion tantalum and/or niobium metal powders and the improved tantalum of performance and/or niobium metal powders and with the electrolytic capacitor anode of this powder manufacturing.
Background technology
Development along with electronics industry, require electronic component high-performance and miniaturization, as slug type tantalum, niobium electrolytic capacitor high unit volume specific capacitance and Unit Weight specific capacitance to be arranged, this just requires to use has higher BET specific area, and promptly the tantalum that primary partical is thinner, niobium powder are made electrolytic capacitor anode.
Tantalum, niobium metal powders carry out with the compound of tantalum niobium metal and reducing agent normally that electronation or compact metal obtain through over hydrogenation powder process.A kind of method obtains before general by the porous basic aggregate of many primary particals (claiming primary particle again) in conjunction with the high-specific surface area of forming, and what a kind of method in back obtained is high-purity still little powder of specific area.
Be used for describing the specific area (m that the physical quantity of metallic thickness has cryogenic nitrogen absorption BET to measure
2/ g), and the Fei Shi average grain diameter (FSSS/ μ m) that the inferior pulp classifier of Fei Shi is measured, the particle diameter of the powder that the laser particle size distribution instrument is measured distributes, the particle morphology size of SEM and determination of transmission electron microscopy.The BET specific area measuring be the reflection primary partical size.The primary partical of tantalum powder is thin more, and the BET specific area is big more, and general specific volume is also high more.The Fei Shi average grain diameter is that the inferior pulp classifier of Yong Feishi adopts gas permeable method mensuration air to obtain by the flow velocity that is seated in the powder in the metal tube, and is relevant with the size of particle, also relevant with the cohesive strength of powder on the one hand; And for the metal dust after the cohesion, the powder of different specific areas can have close Fei Shi average grain diameter; For the powder of same grade, the powder Fei Shi average grain diameter that cohesion is good is bigger.The laser particle size distribution results is to utilize particle that the diffraction and the formed intensity distributions of scattering of laser are drawn, mensuration be that the appearance and size of porous aggregated particle or full particle and particle diameter distribute, and provide D10, D25, D50, D75 and D90 value.The mass percent that on behalf of particle, the corresponding particle size values of D10, D25, D50, D75 and D90 add up from smallest particles respectively reaches the maximum particle diameter value 10%, 25%, 50%, 75% and 90% respectively, wherein the overall particle size of D50 (middle diameter) reflection powder.ESEM can observe submicron order arrive millimetre-sized powder, and transmission electron microscope can be observed nanometer grade powder.
The BET specific area of the former powder of tantalum powder that the sodium reduction potassium floutaramite is produced is at about 0.2～6.0m
2/ g.The about 0.1 μ m (scanning electron microscope observation) of the primary partical average grain diameter of the former powder of 100,000 μ FV/g tantalum powder, its apparent density is about 0.4～0.6g/cm
3The BET specific area of the former powder of tantalum powder that obtains with tantalum oxide reduction is about 1～20m
2/ g, the BET specific area of the former powder of niobium powder that obtains with niobium oxide reduction is about 1～30m
2/ g, their primary partical is in about 10～350nm scope, and apparent density is about 0.4～0.7g/cm
3
Be used to make tantalum powder, the niobium powder of electrolytic capacitor, requiring has good physical property, and for example, powder must have suitable apparent density and good flowability.Immobilising powder is difficult to compression moulding, and the briquet of suppressing with mobile bad metal dust can bring many problems, and is inconsistent as briquet weight, causes every capacitor volume deviation big, and the density unevenness of briquet is even, lining electrolyte and cathode material difficulty.Therefore, the flowing velocity that expectation is used to make the tantalum powder of electrolytic capacitor is greater than 2.0g/sec, and the flowing velocity of niobium powder is greater than 1.0g/sec.
Yet the primary partical of tantalum powder is thin more, and flowability is more bad, so the attritive powder that sodium reduction will be obtained (basic aggregate) is condensed into suitable apparent density of having of porous and the powder that good flowability is arranged.
Also have, enough intensity will be arranged at the briquet that tantalum, niobium powder are pressed into; When sintering briquet into electrolytic capacitor anode, require to have suitable porosity to distribute and bigger hole, so that can fully flood manganese nitrate solution, the MnO that thermal decomposition forms
2With the abundant covering dielectric oxide-film of cathode material ability, increase capacity, too big hole is unfavorable to the equivalent series resistance (ESR) that reduces electrolytic capacitor.
People always are being that the physical property of improving tantalum powder, niobium powder has been done many effort always.World patent WO 99/61184 discloses a kind of method of metallic cohesion and metal dust that improves its performance of making, this method is that handle can be vaporized or the liquid of volatile combines the formation wet powder with metallic, vibration or closely knit wet powder, with the wet powder dried cake, form flocculated particle after the heat treatment.Unfortunately, because the powder of making like this is polygonal, making tantalum powder, the niobium powder that specific volume is higher than 80000 μ FV/g with this method, its flowability seems not good enough.
Also have, occur the superimposed of the face of sheet powder and face when vibrating easily, reduce its voidage, and can influence briquet intensity at flaked tantalum powder that will be wet (primary partical is a sheet---width is 1～60 with the ratio of thickness).In addition, be the fine powder of reuniting because flaked tantalum powder do not resemble that electronation obtains, produce according to the method described above and be difficult to reach enough big briquet intensity.
The production method of pelletized tantalum powder that Chinese patent CN1238251A is disclosed, but owing to there not be to adopt the step smash former powder, the pelletized tantalum powder that the tantalum powder raw material powder that condenses greater than the basic aggregate of 50 μ m for middle diameter is made mobile bad; From accompanying drawing 3 and table 2 as seen, the primary partical size of employed tantalum powder is relatively large, and the specific volume of the pelletized tantalum powder of acquisition is lower than 80000 μ FV/g, is difficult to be applicable to make the high-performance electrolytic capacitor anode.
Summary of the invention
In order to address the above problem, the inventor is by the discovery of concentrating on studies, if basic aggregate is thin more, the sphericity of the particle that condenses by granulation is good more, and the flowability of powder is also good more.
In order to overcome the problems referred to above, the invention provides the method for a kind of nodularization granulation, cohesion metal dust.The step that this method comprises has: diameter carried out the metal dust that nodularization granulation and heat-coagulation obtain good fluidity then less than the fine powder of 50 μ m during metallic was broken into.
One aspect of the present invention, an instantiation of the method for the present invention's group metal dust may further comprise the steps:
(a) metal dust is smashed D50 less than 50 μ m, preferably less than the fine metal dust of 30 μ m;
(b) making the broken refining metallic powder that contains volatile liquid, is tantalum and/or niobium powder as main component, and wet spheric granules is made in the nodularization granulation;
(c), remove volatile liquid and manufacture and increased the pre-flocculated particle of flowing of density with the wet static oven dry of spheric granules;
(d) above-mentioned pre-flocculated particle is heat-treated under vacuum;
(e) the heat treatment powder that sieves obtains flowable cohesion metal dust.
Another aspect of the present invention provides a kind of cohesion metal dust of flowable porous, and improved tantalum of a kind of performance and/or niobium metal or its alloy powder particularly are provided.Described cohesion tantalum powder has the 2.0g/sec of being at least flowing velocity, about 0.2～6.0m
2The BET specific area of/g is not less than the Fei Shi average grain diameter of 1.0 μ m, 1.2～5.5g/cm
3Apparent density; Described cohesion niobium powder has the 1.0g/sec of being at least flowing velocity, about 0.5～8.0m
2The BET specific area of/g is not less than the Fei Shi average grain diameter of 1.0 μ m, 0.7～3.5g/cm
3Apparent density.Described tantalum and/or niobium metal powders are to have the sintered body pore-size distribution is improved and improve briquet intensity.
The invention still further relates to the electrolytic capacitor anode made from the tantalum powder and/or the niobium powder of the inventive method manufacturing, its specific volume is 5,000～300,000 μ FV/g.
In the present invention, provide following technical scheme:
In the 1st technical scheme, provide a kind of nodularization granulation cohesion metal dust especially to wrap
The method of drawing together the metal dust of tantalum or niobium may further comprise the steps:
(a) metal dust is especially comprised the metal dust of tantalum or niobium smash form in diameter D50 less than 50 μ m, especially less than the fine metal dust of 30 μ m;
(b) will contain the broken fine metal dust of volatile liquid, be the powder of tantalum, niobium or their alloy as main component, preferably adopts comminutor to be a granulated into wet granular;
(c) with the static oven dry of wet granular, remove volatile liquid and manufacture the particle diameter that increased density less than 1000 microns, preferably less than 500 microns free-pouring pre-flocculated particle;
(d) above-mentioned free flowing granule is heat-treated;
(e) the heat treatment powder that sieves obtains flowable cohesion metal dust.
In the 2nd technical scheme, a kind of method according to above-mentioned the 1st technical scheme is provided, the liquid in the wherein said step (b) is the deionized water or the aqueous solution.
In the 3rd technical scheme, a kind of method according to above-mentioned the 1st technical scheme is provided, the amount of the liquid that powder contains in the wherein said step (b) is 2%～50% of a powder weight, preferably 5%～40%.
In the 4th technical scheme, provide a kind of method, 50～200 ℃ in vacuum drying chamber Rio oven dry of the drying of the wet granular of the granulation in the wherein said step (c) at least 16 hours and finishing according to above-mentioned the 1st technical scheme.
In the 5th technical scheme, a kind of method according to above-mentioned the 1st technical scheme is provided, the ratio of the apparent density of the former powder before the apparent density of wherein said pre-flocculated particle and the granulation is preferably 1～4 greater than 1, and more preferably 1.5～2.5.
In the 6th technical scheme, a kind of method according to above-mentioned the 1st technical scheme is provided, wherein said step (d) comprises 20～60 minutes the vacuum heat of insulation under 850～1700 ℃, preferred 900～1400 ℃ with tantalum powder and/or niobium powder.
In the 7th technical scheme, the flowable cohesion tantalum powder that provides a kind of each method according in above-mentioned the 1st～6 technical scheme to obtain, described cohesion tantalum powder for example comprise and are similar to spherical flocculated particle.
In the 8th technical scheme, a kind of cohesion tantalum powder according to above-mentioned the 7th technical scheme is provided, the flowing velocity that described tantalum powder has is at least about 2.0g/sec, is preferably about 4～6g/sec.
In the 9th technical scheme, a kind of cohesion tantalum powder according to above-mentioned the 7th technical scheme is provided, described tantalum powder has the above Fei Shi average grain diameter of 1.0 μ m.
In the 10th technical scheme, a kind of cohesion tantalum powder according to above-mentioned the 7th technical scheme is provided, described tantalum powder contains a kind of element in O, N, P, B, the Si group at least, especially comprises at least a in the following composition: about 0.12%～3% oxygen and about 0.005%～10% nitrogen.
In the 11st technical scheme, a kind of cohesion tantalum powder according to above-mentioned the 7th technical scheme is provided, the BET specific area that described tantalum powder has is about 0.2～6.0m
2/ g, more preferably about 0.8～3.5m
2/ g.
In the 12nd technical scheme, a kind of cohesion tantalum powder according to above-mentioned the 7th technical scheme is provided, the apparent density that described tantalum powder has is about 1.2～5.5g/cm
3, be more preferably 1.5～2.0g/cm
3
In the 13rd technical scheme, a kind of cohesion niobium powder that obtains according to each the described method in above-mentioned the 1st～6 the middle technical scheme is provided, described cohesion niobium powder for example comprises the particle that is similar to sphere.
In the 14th technical scheme, a kind of cohesion niobium powder according to above-mentioned the 13rd technical scheme is provided, the flowing velocity that described cohesion niobium powder has is at least about 1.0g/sec, more preferably about 2.5～4g/sec.
In the 15th technical scheme, a kind of cohesion niobium powder according to above-mentioned the 13rd technical scheme is provided, described cohesion niobium powder has the above Fei Shi average grain diameter of 1.0 μ m.
In the 16th technical scheme, a kind of cohesion niobium powder according to above-mentioned the 13rd technical scheme is provided, described cohesion niobium powder contains a kind of element in O, N, P, B, the Si group at least, especially comprises at least a in the following composition: the oxygen of about 0.3wt%～12wt% and be the nitrogen of about 0.01wt%～10wt%.
In the 17th technical scheme, a kind of cohesion niobium powder according to above-mentioned the 13rd technical scheme is provided, the BET specific area that described niobium powder has is about 0.5～8.0m
2/ g is preferably about 1.0～4.5m
2/ g.
In the 18th technical scheme, a kind of cohesion niobium powder according to above-mentioned the 13rd technical scheme is provided, the apparent density that described niobium powder has is about 0.7～2.5g/cm
3, preferably be about 1.0～1.6g/cm
3
In the 19th technical scheme, a kind of cohesion tantalum powder or niobium powder according to the above-mentioned the 7th or the 13rd technical scheme is provided, described tantalum powder or niobium powder are to comprise powder granular and/or the sheet primary partical.
In the 20th technical scheme, the method for a kind of nodularization granulation cohesion tantalum and/or niobium metal powders is provided, may further comprise the steps:
(a) tantalum and/or niobium metal powders are smashed middle diameter D50 less than 50 μ m, especially less than the fine metal dust of 30 μ m;
(b) with volatile liquid and broken refining metallic powder, be the powder of tantalum, niobium or their alloy as main component, granulation manufactures wet particle;
(c), remove volatile liquid and manufacture and increased the free-pouring of density, preferably less than the pre-flocculated particle of 500 μ m less than 1000 μ m with the wet static oven dry of particle;
(d) above-mentioned pre-flocculated particle is heat-treated;
(e) metal dust that sieves and obtain condensing.
In the 21st technical scheme, providing a kind of is the capacitor anode of 5000～250000 μ FV/g by the specific capacitance according to each described tantalum powder manufacturing in above-mentioned the 7th～the 12nd and the 19th technical scheme, is the capacitor anode of 10000～300000 μ FV/g by the specific capacitance according to each described niobium powder manufacturing in above-mentioned the 13rd～the 19th technical scheme perhaps.
Description of drawings
Fig. 1 is the stereoscan photograph after the former powder process of the embodiment of the invention 1 is smashed.
Fig. 2 is the stereoscan photograph of the pre-flocculated particle of the dispersion after the embodiment of the invention 1 nodularization granulation.
Fig. 3 is the stereoscan photograph of the tantalum powder after the embodiment of the invention 1 heat-coagulation and the deoxidation.
Fig. 4 is the stereoscan photograph of comparative example 1 tantalum powder.
Fig. 5 is the surface scan electromicroscopic photograph of the sintered body made of the tantalum powder of embodiment 1.
Fig. 6 is the surface scan electromicroscopic photograph of the sintered body made of the tantalum powder of comparative example 1.
Fig. 7 a, 7b are the stereoscan photographs of the tantalum powder different multiplying after the embodiment of the invention 2 heat-coagulations and the deoxidation.
Fig. 8 a is the particle cross section of embodiment 3 flaked tantalum powders, and 8b, 8c are the pattern stereoscan photographs of the flaked tantalum powder after embodiment 3 heat-coagulations and the deoxidation.
Fig. 9 is the stereoscan photograph of comparative example 3 tantalum powder patterns.
Figure 10 is the stereoscan photograph of embodiment 4 niobium powder patterns.
Figure 11 is the stereoscan photograph of embodiment 5 tantalum powder patterns.
Figure 12 is the comparison of the pore-size distribution of embodiment 1 and comparative example 1 tantalum powder sintering body.
Figure 13 is that the particle diameter of embodiment 2 raw meal (curve 1), broken former powder (curve 2) and nodularization granulation cohesion tantalum powder (curve 3) distributes relatively.
Figure 14 is the comparison of the briquet intensity of the flaked tantalum powder that obtains of embodiment 3 and comparative example 3.
The specific embodiment
An embodiment that relates to nodularization granulation cohesion metal powder method of the present invention comprises the following steps:
(a) metal dust is smashed D50 less than 50 μ m, preferably less than the fine metal dust of 30 μ m;
(b) make the broken refining metallic powder that contains volatile liquid, as tantalum and/or niobium powder, nodularization is a granulated into wet granular;
(c) with the static oven dry of wet granular, remove volatile liquid and manufacture dispersion increase the free-pouring pre-flocculated particle of density;
(d) more above-mentioned pre-flocculated particle is heat-treated under vacuum;
(e) the heat treated powder that sieves obtains flowable cohesion metal dust.
For reaching the object of the invention, metal dust can be the powder of any kind, and for example metal, alloy, mixture etc. are not limited to this.The metal dust example comprises tantalum powder, niobium powder, iron powder, cobalt powder, titanium valve etc. and the alloy powder of described metal and their mixture.Preferred metal dust comprises tantalum powder and/or niobium powder or is the metal dust or the tantalum-niobium alloy powder of main component with tantalum and/or niobium, or their mixture.
According to the inventive method, preferred metal dust raw material is tantalum powder and/or niobium powder or their alloy powder.For for the tantalum powder raw material that condenses, its BET specific area is at least about 0.3m
2/ g is preferably about 0.5～20m
2/ g.For for the niobium powder raw material that condenses, its BET specific area is at least about 0.6m
2/ g is preferably 1.0～30m
2/ g.Described metal dust is a porous.To the shape of metal dust without limits, can be coralliform, botryoidalis aggregate particle or granular, sheet, horn shape or their any combination.
According to the inventive method, described tantalum powder and/or niobium powder can be tantalum powder, the niobium powder that sodium metal reduction potassium floutaramite, potassium niobate fluoride obtain; The oxide of tantalum and/or niobium is reduced (making reducing agent as magnesium, calcium, magnesium hydride, calcium hydride, sodium etc.) or the halide of tantalum and/or niobium is reduced tantalum powder, the niobium powder that (hydrogen, sodium, potassium etc. are made reducing agent) obtains; And the compact metal of tantalum and/or niobium, as ingot, behind over hydrogenation, grind powder or its alloy powder of making, but be not limited to this.
According to the inventive method, described tantalum powder and/or niobium powder can be to be used to make the high specific volume powder of low-voltage (being lower than 20V) electrolytic capacitor or to be used to make middle and high voltage (flaked tantalum powder of electrolytic capacitor of 20V～100V) or tantalum and/or the niobium powder that method for hydrogenation makes.
According to the inventive method, the method that metal dust is smashed can stir (as 100～500 rev/mins) to metal dust in the tank high speed that plate washer is arranged, and adopts vibration of ultrasonic wave, and bigger particle (basic aggregate) is broken into than fine powder; Also can adopt broken powder process of hydrogenation or abrasive method to make attritive powder, but be not limited thereto.The middle diameter D50 of the attritive powder after described the smashing is less than 50 μ m, preferably less than 30 μ m.
According to the inventive method, the nodularization granulation step can will contain the broken refining metallic powder of volatile liquid, and for example the powder of tantalum and/or niobium through vibration, rock and roll, extruding, makes it increase density, makes wet spheric granules.Described volatile liquid can be the liquid of any proterties, for example, water, moisture liquid, contain ethanol liquid, contain aromatic liquid and their mixing material etc., but be not limited thereto.Preferred volatile liquid is deionized water.In order to reach certain purpose, any chemicals that help controlling the shrinkage factor of powder when high temperature sintering and reduce surface area losses that can add desired ratio in pulverizing process are in liquid, as the chemical substance of phosphorous, the nitrogen that burns agent as resistance, boron, oxygen.Can add from about 0.0001% to about 0.05% phosphorus, the boron element at least a according to the weight metal meter.
According to the inventive method, the described refining metallic powder that contains volatile liquid is to utilize the surface tension of liquid to increase interparticle cohesiveness, and the nodularization granulation forms density even metal powder particle.Metal dust contains the amount of liquid, is about 2%～50% of metal dust weight for tantalum powder, niobium powder, is preferably about 5%～40% of tantalum powder, niobium grain weight amount.
According to the inventive method, contain volatile liquid metals powder and can be after reduction pie through smashing, the product of pickling, diafiltration.Bimetallic halide (K as alkali metal reduction tantalum and/or niobium
2TaF
7, K
2NbF
7) product, the product of magnesium-reduced niobium oxide, tantalum oxide or use CaCl
2Add the resulting product of Na reduction-oxidation tantalum or niobium oxide through fragmentation, diafiltration, smash, obtain containing the particle of the broken D50 of arriving that comprises niobium and/or tantalum of volatile liquid after the pickling, diafiltration less than 50 μ m.
According to the inventive method, the described metal dust that contains volatile liquid comprise with liquid join broken to D50 less than 50 μ m, in fact in moisture free dried metal dust, through fully infiltration, the infiltration time was at least about 5 minutes, preferred 20～300 minutes, mix then to reach and contain described liquid equably.Mixed method is had no particular limits, can admix by hand or mechanical agitation with the method for simple hybrid solid and liquid, as mixing with mixer, batch mixer.
According to the inventive method, described nodularization granulation is to make metal dust increase density and nodularization granulation.Described nodularization granulation can be adopted any method that can make powder increase density and form spheric granules; place in the container as the metal dust that will contain liquid; make the mutual extruding between its vibration, rock and roll, the particle and form wet spheric granules, as in the nodularization comminutor, carrying out.
Also have, can carry out once above nodularization granulation cohesion as flaked tantalum powder.
According to the inventive method, the drying of the wet particle after the described nodularization granulation can adopt any method that evaporates that under static state can make in the metal dust, as the basic Back stroke of liquid in the metal dust is sent, as in atmosphere or in the flow air from about 20 ℃ to about 100 ℃ of oven dry at least 24 hours, or in vacuum drying chamber negative pressure state from about 50 ℃ to about 300 ℃ of oven dry at least 16 hours.
The wet particle that disperses is obtained having increased the free-pouring pre-flocculated particle of the dispersion of density after drying.The particle diameter of described pre-flocculated particle can be controlled at less than 1000 microns, preferably less than 500 microns.
According to the inventive method, the ratio of the apparent density of the attritive powder before the apparent density of the described pre-flocculated particle that has increased density and the nodularization granulation is preferably 1～4 greater than 1, and more preferably 1.5～2.5.
According to the inventive method,, heat-treat with that in case make above-mentioned pre-flocculated particle.According to the inventive method, before heat treatment, material phosphorous, boron can be blended in the powder, as adding NH
4H
2PO
4, P
2O
5, (NH
4)
2HPO
4And NH
4PF
6Powder or H
3PO
4, B
2O
3, H
2BO
3
Described heat treatment is the same with other metal dust heat treatment, for example pre-flocculated particle is transferred in the crucible of tantalum or niobium material system, puts it into vacuum heat treatment furnace in the lump and heats, and makes the inner sintering of each pre-flocculated particle and forms flocculated particle.For being the powder of main component with the tantalum, heat treatment temperature from about 900 ℃ to about 1700 ℃ of insulations from about 20 minutes to about 60 minutes.For being the powder of main component with the niobium, heat treatment temperature from about 850 ℃ to about 1400 ℃ of insulations approximately from 20 minutes to about 60 minutes.
According to the inventive method, do not have very strong sintering after the heat treatment between the formed flocculated particle, that is to say obtain be between particle slight bonding and can not form pie.According to the inventive method, heat treated product does not need fragmentation just directly to sieve, and obtains the metal dust that can flow and condense.Sieve and typically use 40 orders～100 purpose sieves.
According to the present invention, the metal dust that has condensed removes partial oxygen if desired, the optional method of knowing altogether according to personnel in the industry, with metal dust and the reducing agent that is lower than 5% (weight metal), mix mutually as Mg, Ca, Al, in vacuum or inert atmosphere, heat-treating pickling then, washing, oven dry to about 1100 ℃ from about 700 ℃.
According to the inventive method, choose wantonly in the process of reduction, heat treatment or deoxidation at the described metal dust that will condense and to mix nitrogen, make tantalum and/or the nitrogenize of niobium metal powders part, the powder nitrogen content is about 0.005%～10%.
According to the inventive method, can obtain having the metal dust that multiple superperformance combines.The cohesion tantalum of the flowable porous spherical that the present invention must fall and/or the meso-position radius of niobium metal particle are about 60～200 μ m.Particularly described cohesion tantalum powder contains oxygen 0.12%～3% (mass ratio), and nitrogenous 0.005%～10% (mass ratio) has flowing velocity and be at least 2.0g/sec, preferred 2.0～6.0g/sec, more preferably 4.0～6.0g/sec; Have and be not less than 1.0 μ m Fei Shi average grain diameters; The BET specific area that has is about 0.2～6.0m
2/ g, preferred about 0.8～3.5m
2/ g; About 1.2～the 5.5g/cm of the apparent density that has
3, preferred about 1.4～2.2g/cm
3Described cohesion niobium powder contains oxygen 0.3%～14%, and nitrogenous 0.01%～10% (mass ratio) has flowing velocity and be at least 1.0g/sec, preferred about 1.0～4.0g/sec, more preferably from about 2.5～4.0g/sec; Have the Fei Shi average grain diameter that is not less than 0.8 μ m, the BET specific area that has is about 0.5～8.0m
2/ g, preferred about 1.0～4.5m
2/ g; The apparent density that has is about 0.7～3.5g/cm
3, preferred about 1.0～1.6g/cm
3
The briquet of suppressing than metal dust in the past with cohesion metal dust of the present invention has higher briquet intensity.The sintered body of the metal powder sintered one-tenth of producing with the inventive method of cohesion has the sintered body pore-size distribution that has improved than the metal dust of additive method production in the past, and is less less than the minute aperture of 0.2 μ m, and the hole of 0.2～0.6 μ m is more.
Tantalum powder and/or niobium powder with the inventive method is made through being pressed into briquet, sinter sintered body into, and then anodic oxidation manufactures the electrolytic capacitor anode that surface coverage has layer oxide film in electrolyte solution.The electrolytic capacitor anode that the cohesion tantalum powder that obtains with the inventive method is made, specific volume at about 5,000 μ FV/g to about 250,000 μ FV/g.The electrolytic capacitor anode that the cohesion niobium powder that obtains with the inventive method is made, specific volume at about 10,000 μ FV/g to about 300,000 μ FV/g.
Disclosed powder data are following tests in this specification: mobile value is the method with reference to CNS GB 1482-84 regulation, flowing velocity is that 50g removes so that 50g metal dust sample flow is the standard funnel required time (branch) in the hole of 5mm through diameter, repeats to average for three times to calculate; Powder does not have flowability and is meant that powder is not past dirty in the funnel of mobile measuring instrument; The apparent density of powder (SBD) is tested according to the method for CNS GB5060-85 regulation and is obtained; The average grain diameter of disclosed powder (FSSS) is tested according to the method for CNS GB 3249-82 regulation and is obtained in this specification; The ASAP2021 type specific surface area measuring instrument that the BET specific area of disclosed powder is to use Micromerities company to produce in this specification is measured; Diameter in the size distribution of the powder that the inventive method makes and the particle (D50) is to record after 60 seconds with ultrasonic vibration with the LS-230 type laser particle size distribution instrument that BECKMANCOULTER company produces; In this specification disclosed microphoto with JSM-5610LV sem observation sample and the photography and obtain; The mesh analysis size distribution of cohesion powder is to measure with reference to the method for ASTM-B-214-86 regulation; Disclosed pore-size distribution is to measure with the Autopore III pore-size distribution instrument of Micromerities company in this specification.
In order further to understand the present invention, below in conjunction with embodiment and accompanying drawing the preferred embodiment of the invention is described, but should be appreciated that these describe just to further specifying the features and advantages of the present invention, rather than to the restriction of claim scope of the present invention.
Embodiment
Embodiment 1
The tantalum powder that the sodium reduction potassium floutaramite obtains (raw material 1) is made raw material, and performance datas such as its BET specific area, apparent density, Fei Shi average grain diameter and size distribution see Table 1.This tantalum powder is through broken with about 300 rev/mins of (hereinafter to be referred as RPM) speed rotation in the tank of baffle plate is housed.The BET specific area of broken powder, apparent density, Fei Shi average grain diameter and size distribution etc. are listed in the table 2, and its microscopic appearance is seen Fig. 1.
Get this broken sample 10kg and put a charging tray into, measure deionized water 3500ml, the NH of 2.1g
4H
2PO
4Dissolve in the phosphorous aqueous solution of formation in the water, should be sprinkled upon on the tantalum powder by the phosphorous aqueous solution, infiltrated 10 minutes.Tantalum powder after the infiltration stirs through artificial, and liquid is absorbed in the hole of tantalum powder equably, carries out the nodularization granulation with comminutor.With the 90 ℃ of oven dry 24 hours in vacuum drying box of the wet powder after the nodularization granulation, form particle diameter less than 1000 microns free-pouring pre-flocculated particle.Its microscopic appearance is seen Fig. 2.Its apparent density and flowing velocity value are listed in the table 3.
The pre-cohesion tantalum powder that then will dry is packed in the tantalum crucible, in its vacuum heat treatment furnace of packing in the lump, is heated to about 1200 ℃ and handled 30 minutes under the vacuum of 1.33Pa with downforce.After the heat treatment, with the 80 mesh sieves bulky powder that sieves ,-80 purpose tantalum powder carry out magnesium-reduced and fall oxygen and handle, and then carry out pickling, diafiltration, oven dry, and sieving obtains condensing the tantalum powder.The pattern of cohesion tantalum powder particles is seen Fig. 3.Its flowing velocity, average grain diameter, apparent density, BET specific area, size distribution and mesh analysis, performance datas such as O, N content are listed in the table 4.
Above-mentioned tantalum powder is pressed into briquet, every briquet grain weight 170mg, the about 4.7mm * 3.3mm of size * 2.2mm, the about 5.0g/cm of density
31300 ℃ of sintering obtained agglomerate in about 20 minutes in the vacuum drying oven Rio with above-mentioned briquet.The stereoscan photograph of agglomerate is seen Fig. 5.The pore-size distribution that records agglomerate is seen among Figure 12.
With described agglomerate about 2 hours of 30V constant voltage in the phosphoric acid solution of about 85 ℃ 0.1% (Vol), carry out anodization and form electrolytic capacitor anode.Record the capacity of described anode, specific volume and DC leakage current are listed in the table 4.
Comparative example 1
Get the sodium reduction tantalum powder raw material 1 tantalum powder 10kg that smashes with embodiment 1 identical process and put a dish into, measure deionized water 3500ml, the NH of 2.1g
4H
2PO
4Dissolve in the water the phosphorous aqueous solution of formation and be sprinkled upon on the tantalum powder infiltration 2 hours.Transfer to after the infiltration evenly and add 300ml deionized water and vibration extruding wet powder in the tantalum crucible again, with wet powder in the vacuum drying box Rio 90 ℃ of oven dry formed the cake piece in 24 hours.Its apparent density is about 2.3g/cm
3The tantalum crucible that described tantalum muffin piece of having dried then will be housed is packed in the vacuum heat treatment furnace, heat-treats according to the condition of embodiment 1.Powder is made in pie powder agglomates fragmentation after the heat treatment, the tantalum powder that obtains carries out magnesium-reduced with embodiment 1 identical condition and falls the oxygen processing, the flowing velocity of resulting tantalum powder, average grain diameter, apparent density, BET specific area, size distribution and mesh analysis, performance datas such as O, N content are listed in the table 4.The pattern of tantalum powder particles is seen Fig. 4.
Above-mentioned tantalum powder is pressed the condition of embodiment 1 and made sintered body, the stereoscan photograph of sintered body is seen Fig. 6.The pore-size distribution that records agglomerate is seen among Figure 12.
Described agglomerate is made anode according to embodiment 1 identical condition, and the specific volume and the DC leakage current of the described anode that obtains are listed in the table 4.
Comparison diagram 3 and Fig. 4, as can be seen, the metal dust of making according to the inventive method (Fig. 3) comprises the particle with the sphere of being similar to, and the particle of comparative example 1 is polygonal.Comparison diagram 5 and Fig. 6, as can be seen, the sintered body of making according to the present invention (Fig. 5) has uniform hole, and the intergranular macropore of groupization helps flooding manganese nitrate solution; Comparative example sintered body (Fig. 6) disappearance corner angle, and some surface pore is blocked.Embodiment 1 compares with the performance data of the sample of comparative example 1 from table 4, and the distribution of metal dust particle diameter is more concentrated made in accordance with the present invention, and less+80 purpose meal and less-325 order attritive powders are arranged, and is mobile better.
From Fig. 12 as can be seen, use the pore-size distribution of the tantalum powder sintering anode that the pore-size distribution of the anode of the tantalum powder sintering that makes according to the embodiment of the invention 1 makes than comparative example 1 more concentrated, 0.2 the hole of～0.6 μ m is more, minute aperture less than 0.2 μ m is less, hole greater than 1.0 μ m is also less, help being covered electrolyte and cathode material help reducing the ESR value of electrolytic capacitor.
The tantalum powder that the sodium reduction potassium floutaramite obtains (raw material 2) is made raw meal.In characteristic values such as its BET specific area, apparent density, Fei Shi average grain diameter and size distribution such as the table 1, the size distribution of former powder is seen curve 1 among Figure 13.Through the tantalum powder after broken, the diafiltration of about 300RPM, the oven dry in water, its BET specific area, apparent density, Fei Shi average grain diameter, particle size distribution characteristics are listed in the table 2, and the size distribution curve of broken powder is seen the curve 2 of Figure 13.
Get above-mentioned broken tantalum powder 10kg and put charging tray into, measure deionized water 3500ml, the NH of 5.3g
4H
2PO
4Dissolve in the phosphorous aqueous solution of formation in the water, the aqueous solution that this is phosphorous is sprinkled upon on the tantalum powder and infiltrated 60 minutes.Powder after the infiltration carries out the nodularization granulation according to the method for embodiment 1, with the 80 ℃ of oven dry 24 hours in the vacuum drying box Rio of the wet powder after the nodularization granulation, forms particle diameter less than 1000 microns free-pouring pre-flocculated particle.The apparent density and the flowing velocity of pre-flocculated particle are listed in the table 3.
Then described pre-cohesion tantalum powder of having dried is packed in the tantalum crucible, again it is packed in the lump in the vacuum heat treatment furnace, form cohesion powder in 1050 ℃ of heat treatments 30 minutes at 1.33Pa under with the vacuum of downforce, after coming out of the stove the bulky powder after the heat treatment is sieved, the tantalum powder of cohesion carries out magnesium-reduced according to embodiment and falls the oxygen processing.Flowing velocity, average grain diameter, apparent density, BET specific area, size distribution and the mesh analysis of cohesion powder, performance datas such as O, N content are listed in the table 4.Fig. 7 a, 7b are the different enlargement ratio microstructures of flocculated particle.The size distribution curve of cohesion tantalum powder is seen curve 3 among Figure 13.
Above-mentioned tantalum powder is pressed into briquet, every grain weight 100mg, the about 3mm of the diameter of briquet, high about 2.83mm, the about 5.0g/cm of briquet density
3, briquet 1200 ℃ of sintering in vacuum drying oven were obtained agglomerate in 20 minutes.With described agglomerate 20V constant voltage 2 hours in the phosphoric acid solution of 80 ℃ 0.1% (Vol), carry out anodization and form anode, the specific volume and the DC leakage current of described anode listed in the table 4.
Comparative example 2
Use the performance data of tantalum powder raw material 2 among the embodiment 2 to list in table 1.Get above-mentioned not broken tantalum powder 10kg group processing in advance, pre-groupization powder does not have flowability, and its apparent density sees Table 3.Carry out heat-coagulation according to embodiment 2 identical methods again and fall the oxygen processing, the flowing velocity of the tantalum powder that obtains, average grain diameter, apparent density, BET specific area, size distribution and mesh analysis, performance datas such as O, N content are listed in the table 4.
Above-mentioned tantalum powder is made anode according to embodiment 2 identical conditions, and the specific volume and the DC leakage current of the described anode that obtains are listed in the table 4.
From the result of table 2, the pre-flocculated particle of embodiment 2 has flowability as can be seen, and the pre-flocculated particle of comparative example 2 does not have flowability.The flowing velocity of embodiment 2 tantalum powder is greater than the flowing velocity of comparative example 2 tantalum powder in the table 4.
Embodiment 3
With grinding to form flake powder as raw material in the table 13, oven dry obtains the tantalum powder after the diafiltration, and its BET specific area, apparent density, Fei Shi average grain diameter and size distribution etc. are listed in the table 2.It is many to find that BET specific area through the tantalum powder after grinding has increased, and Fig. 8 a is this cross-sectional scans electromicroscopic photograph that the average compression in back is about 8.6 platy particle that grinds.
With 10 kilograms of tantalum powder after the above-mentioned grinding; add deionized water 600ml; infiltrate and stir after 30 minutes; carry out the nodularization granulation with the nodularization comminutor; 100 ℃ of insulations were dried in 24 hours in the vacuum drying box Rio then; then be lower than under the vacuum of 1.33Pa 1300 ℃ of heat treatments 30 minutes, sieving with 100 mesh sieves and once condensed sheet-like particle tantalum powder.Above-mentioned-100 orders are once condensed the tantalum powder to be poured in the dish; deionized water 2200ml is joined on the tantalum powder infiltration 30 minutes; carry out the nodularization granulation once more with the nodularization comminutor after stirring; with the wet powder after the nodularization granulation in the vacuum drying box Rio 100 ℃ the oven dry 24 hours; form particle diameter less than 1000 microns free-pouring pre-flocculated particle, its apparent density and flowing velocity are listed in the table 3.
Then described pre-cohesion flaked tantalum powder of having dried is packed in the tantalum crucible, pack in the lump again in the vacuum heat treatment furnace, 1.33Pa with the vacuum of downforce under in 1460 ℃ of heat treatments 40 minutes, bulky powder after the heat treatment is sieved with 80 mesh sieve,-80 purpose tantalum powder add the magnesium powder and fall the oxygen processing, then carry out pickling, diafiltration, oven dry, sieving obtains the flaked tantalum powder of secondary aggregation.Fig. 8 b and 8c are the stereoscan photographs of the different multiplying of porous microstructure cohesion tantalum powder, its flowing velocity, average grain diameter, apparent density, BET specific area, size distribution and mesh analysis, and performance datas such as O, N content are listed in the table 4.
With above-mentioned flaked tantalum powder compression moulding, every briquet powder 300mg is the mould of 4.1mm with diameter, and briquet density is respectively 5.0g/cm
3, 5.5g/cm
3, 6.0g/cm
3And 6.5g/cm
3, briquet is carried out briquet intensity (power when briquet is crushed, unit is N) experiment on RGD-05 pressure experiment machine, experimental result is as shown in figure 14.
The flaked tantalum powder of above-mentioned secondary aggregation is pressed into briquet, every briquet grain weight 150mg, the about 3mm of briquet diameter, high about 4.25mm, the about 5.0g/cm of briquet density
3, 1500 ℃ of sintering obtained agglomerate in 30 minutes in vacuum drying oven.With described agglomerate 140V constant voltage 2 hours in the phosphoric acid solution of about 80 ℃ 0.1% (Vol), carry out anodization and form electrolytic capacitor anode, the specific volume and the DC leakage current of described anode listed in the table 4.
Comparative example 3
With embodiment 3 flaked tantalum powder 10kg,, after fragmentation, sieve and obtain heat treatment tantalum powder one time with 100 mesh sieves 1300 ℃ of heat treatments 30 minutes through the raw material 3 that grinds.Then a heat treatment tantalum powder is packed in the tantalum crucible, poured the 3600ml deionized water dipping into 6 hours on the tantalum powder in the crucible, the tantalum crucible that vibration is fixed on the table makes wet tantalum powder closely knit, dried 24 hours for 100 ℃ in the vacuum drying box Rio, form piece, this tantalum crucible that caking tantalum powder is housed is heat-treated according to embodiment 3 identical conditions, " tantalum cake " fragmentation of will luming after coming out of the stove, cross 80 mesh sieves, according to embodiment 3 the same terms oxygen is fallen in-80 order powder then, the pattern of the tantalum powder particles that obtains is seen Fig. 9.The average grain diameter of tantalum powder, apparent density, BET specific area, size distribution, mesh analysis and flowing velocity, performance datas such as O, N content are listed in the table 4.
Carry out the briquet strength test with above-mentioned tantalum powder and embodiment 3 are the same, experimental result as shown in figure 14.At 5.0g/cm
3～6.5g/cm
3Pressed density under, use according to the crushing strength of the briquet of the tantalum powder compacting of the inventive method preparation all than the height of comparative example 3.
Above-mentioned tantalum powder is listed in the table 4 according to the experimentize specific volume and the electric property such as DC leakage current of test of embodiment 3 the same terms.
Comparison diagram 8b and Fig. 9, as can be seen, the flocculated particle according to the inventive method preparation of Fig. 8 b comprises similar spheric granules, and than the uniform particles of the comparative example among Fig. 93.The tantalum powder of learning embodiment 3 from the data of table 4 has less+80 order meal and-325 order fine powders compared with comparative example 3, and better flowability is arranged.
Embodiment 4
BET specific area, apparent density, Fei Shi average grain diameter and the size distribution etc. of the niobium powder that the magnesium-reduced niobium oxide obtains (raw material 4) are listed in the table 1.Rotate through about 400RPM speed in the tank of baffle plate is housed the niobium powder is smashed, BET specific area, apparent density, Fei Shi average grain diameter and the size distribution etc. of the former powder of niobium powder after broken are listed in the table 2.
Get described niobium powder 10kg and put charging tray into, will contain the NH of 500mg
4H
2PO
4Deionized water 3500ml solution be sprinkled upon on the niobium powder, infiltrated 30 minutes, liquid is infiltrated up in the niobium powder hole equably, carry out the nodularization granulation with comminutor.With the 90 ℃ of oven dry 24 hours of the wet powder after the nodularization granulation, form particle diameter less than 1000 microns free-pouring pre-flocculated particle in the vacuum drying box Rio.The apparent density and the flowing velocity of pre-cohesion powder are listed in the table 3.
Then described pre-cohesion niobium powder of having dried is packed in the niobium crucible, again it is packed in the lump in the vacuum heat treatment furnace, 1.33Pa with the vacuum of downforce under in 1040 ℃ of heat treatments 30 minutes, bulky powder after the heat treatment is crossed-80 order niobium powder that 80 mesh sieves obtain fall oxygen and handle, then carry out pickling, diafiltration, oven dry.The pattern of cohesion niobium powder particles is seen Figure 10.Its flowing velocity, average grain diameter, apparent density, BET specific area, size distribution and mesh analysis, performance datas such as O, N content are listed in the table 4.
Above-mentioned niobium powder is pressed into briquet, every briquet grain weight 80mg, the about 3mm of briquet diameter, high about 3.8mm, the about 3.0g/cm of briquet density
3, 1150 ℃ of sintering obtained agglomerate in 20 minutes in vacuum drying oven.
With described agglomerate 30V constant voltage 4 hours in the phosphoric acid solution of 80 ℃ 0.1% (Vol), carry out anodization and form electrolytic capacitor anode, the specific volume and the DC leakage current of described anode listed in the table 4.
Embodiment 5
With sodium metal and CaCl
2BET specific area, apparent density, Fei Shi average grain diameter and the size distribution etc. of the tantalum powder that the reduction-oxidation tantalum obtains (raw material 5) are listed in the table 1.About 200RPM in water smashes with above-mentioned tantalum powder; starchiness tantalum powder is added ethanol (make it contain ethanol: the mass ratio of water is about 1: 1 ethanol water) to be dried (the dry performance data of sampling is listed in the table 2) with filter centrifugal and contains ethanol water reach the tantalum powder in the tantalum powder: the ethanol water mass ratio is about 1: 0.10～degree of 0.25 (moisture high speed tester mensuration) till; then the above-mentioned tantalum powder that contains ethanol water is carried out the nodularization granulation with comminutor; form wet granular; with the 60 ℃ of oven dry 24 hours of the wet granular after the nodularization granulation, form particle diameter less than 1000 microns free-pouring pre-flocculated particle in the vacuum drying box Rio.The apparent density of pre-cohesion powder and mobile value are listed in the table 3.
Then provide the phosphorus source with sneaking into ammonium hexafluorophosphate in the described pre-cohesion tantalum powder of having dried, make the phosphorous 120ppm of tantalum, the powder that will the produce phosphorus then tantalum crucible of packing into, in its vacuum heat treatment furnace of packing in the lump, 1.33Pa with the vacuum of downforce under in 1060 ℃ of heat treatments 30 minutes, the bulky powder after the heat treatment is sieved with 80 mesh sieve ,-80 order tantalum powder that obtain carry out magnesium and fall oxygen and handle, then carry out pickling, diafiltration, oven dry, sieving obtains the product powder.Its flowing velocity, average grain diameter, apparent density, BET specific area, size distribution and mesh analysis, performance datas such as O, N content are listed in the table 4.The ESEM microphoto of tantalum powder as shown in figure 11.
Above-mentioned tantalum powder is pressed into briquet, every briquet grain weight 40mg, the briquet size is: 2.62mm * 2.22mm * 1.45mm, the about 4.74g/cm of density
3The cuboid briquet, this briquet 1200 ℃ of sintering in vacuum drying oven were obtained agglomerate in 20 minutes.With described agglomerate 16V constant voltage 2 hours in the phosphoric acid solution of 60 ℃ 0.01% (Vol), carry out anodization and form electrolytic capacitor anode, the specific volume and the DC leakage current of described anode listed in the table 4.
In characteristic values such as BET specific area, apparent density, Fei Shi average grain diameter and the size distribution of the tantalum powder that the sodium reduction potassium floutaramite obtains (raw material 6) such as the table 1.With this raw meal through in water with ultrasonic wave smash, tantalum powder after the diafiltration, oven dry, its BET specific area, apparent density, Fei Shi average grain diameter, particle size distribution characteristics are listed in the table 2.Get above-mentioned broken tantalum powder 500g and put charging tray into, measure deionized water 180ml, the NH of 0.35g
4H
2PO
4Dissolve in the phosphorous aqueous solution of formation in the water.The aqueous solution that this is phosphorous is sprinkled upon on the tantalum powder and infiltrated 60 minutes; after manually stirring; carry out the nodularization granulation with the nodularization comminutor; with the wet powder after the nodularization granulation in the vacuum drying box Rio 60 ℃ the oven dry 24 hours; form particle diameter less than 1000 microns free-pouring pre-flocculated particle, its apparent density and flowing velocity are listed in the table 3.
Then described pre-cohesion tantalum powder of having dried is packed in the tantalum crucible, again it is packed in the lump in the vacuum heat treatment furnace, 30 minute carry out change a processing in 1050 ℃ of heat treatments at 1.33Pa under with the vacuum of downforce, form the cohesion powder, sieve with the bulky powder of 100 mesh sieve after with heat treatment ,-100 purpose tantalum powder carry out magnesium-reduced and fall oxygen and handle, and carry out nitrating, then carry out pickling, diafiltration, oven dry, sieving obtains the product powder.Its flowing velocity, average grain diameter, apparent density, BET specific area, size distribution and mesh analysis, performance datas such as O, N content are listed in the table 4.
Above-mentioned tantalum powder is pressed into briquet, every grain weight 100mg, the about 3.00mm of the diameter of briquet, high about 2.83mm, the about 5.0g/cm of briquet density
3Briquet 1250 ℃ of sintering in vacuum drying oven were obtained agglomerate in 20 minutes.With described agglomerate 10V constant voltage 2 hours in the phosphoric acid solution of 80 ℃ 0.1% (Vol), carry out anodization and form electrolytic capacitor anode, the specific volume and the DC leakage current of described anode listed in the table 4.
Table 1 example material powder of the present invention characteristic value
| Raw material 1/ sodium reduction tantalum powder | | Raw material 3/ sodium reduction tantalum powder | Raw material 4/ sodium reduction niobium powder | Raw material 5/ tantalum oxide reduction tantalum powder | | |
| FSSS (μ m) apparent density (g/cm 3) BET(m 2/ g) flow velocity, (g/sec) powder size distributes, (μ m) D10 D25 D50 D75 D90 | 0.38 0.51 1.80 does not have 4.929 17.36 65.23 109.5 151.2 | 0.27 0.57 3.30 does not have 3.340 10.43 59.53 98.99 149.6 | 2.51 1.68 0.60 do not have 25.81 53.55 108.0 155.5 205.4 | 0.54 0.46 1.88 does not have 4.730 11.28 51.12 105.9 163.0 | 0.26 0.54 6.80 does not have 2.382 11.23 50.52 105.9 163.2 | 0.23 0.60 5.10 does not have 2.730 11.28 51.53 78.99 109.6 |
The broken back of table 2 raw material characteristic value
| Embodiment 1 | Comparative example 1 | | Comparative example 2 | Embodiment 3 | Comparative example 3 | Embodiment 4 | Embodiment 5 | | |
| FSSS (μ m) apparent density (g/cm 3) BET(m 2/ g) powder size (μ m) D10 D25 D50 D75 D90 that distributes | 0.36 0.50 1.96 1.154 3.283 19.68 70.23 103.3 | 0.36 0.50 1.96 1.154 3.283 19.68 70.23 103.3 | 0.26 0.55 3.52 1.074 2.916 7.803 23.42 53.78 | 0.27 0.57 3.30 3.34 10.43 59.53 98.99 149.6 | 0.35 0.72 0.88 2.731 7.580 25.36 78.59 114.9 | 0.35 0.72 0.88 2.731 7.580 25.36 78.59 114.9 | 0.52 0.48 2.01 2.871 5.183 19.22 59.23 102.7 | 0.2 0.56 7.7 1.353 2.030 3.309 6.344 15.11 | 0.23 0.61 5.20 1.112 2.135 6.520 21.10 62.30 |
Characteristic after the table 3 nodularization granulation
| Embodiment 1 | Comparative example 1 | | Comparative example 2 | Embodiment 3 | Comparative example 3 | Embodiment 4 | Embodiment 5 | | |
| Granulation density (g/cm 3) flow velocity (g/sec) | 1.28 2.50 | 2.3 (piece) do not have | 1.15 2.0 | 0.98 do not have | 1.31 3.12 | 2.2 (piece) do not have | 0.72 2.1 | 1.31 2.78 | 1.12 2.0 |
Table 4 nodularization granulation cohesion back powder characteristics
| Embodiment 1 | Comparative example 1 | Embodiment 2 | Comparative example 2 | Embodiment 3 | Comparative example 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | |
| FSSS (μ m) apparent density (g/ cm 3) BET(m 2/ g) powder size (μ m) D10 D25 D50 D75 D90 mesh analysis (%)-60/+80-80/+200-200/+325-325/+400-400 flowability (g/sec) O (%) N (%) electrolytic capacitor anode grain weight (mg) briquet density (g/cm that distributes3) sintering temperature (℃) sintering time (min) sintered density (g/cm 3) the formation liquid temp (℃) formation voltage (V) specific volume (μ FV/g) DC leakage current (nA/CV) | 2.8 1.78 1.68 28.72 55.85 104.4 159.4 208.2 0.8 52.6 24.3 12.5 9.8 3.85 0.50 0.07 170 5.0 1300 20 5.40 85 30 86500 0.65 | 3.0 1.80 1.65 15.22 35.81 75.02 162.4 270.3 3.6 35.4 23.6 13.5 23.9 1.78 0.51 0.07 170 5.0 1300 20 5.41 85 30 85400 0.66 | 1.52 1.45 2.56 34.52 60.03 105.5 163.3 216.1 3.0 60.2 19.1 11.5 6.2 3.33 0.860 0.32 100 5.0 1200 20 5.10 80 20 151800 0.72 | 1.02 1.30 2.57 17.96 39.21 82.58 134.6 181.3 3.5 40.6 19.6 14.5 21.8 1.37 0.850 0.30 100 5.0 1200 20 5.12 80 20 145010 0.74 | 2.88 1.81 0.62 6.88 35.47 93.54 190.5 268.1 1.8 37.6 23.5 12.5 24.6 4.16 0.212 0.021 150 5.0 1500 30 5.46 80 140 19800 0.32 | 2.91 1.80 0.61 7.02 32.51 100.2 196.3 286.1 2.5 28.6 14.2 16.8 37.9 1.92 0.220 0.022 150 5.0 1500 30 5.50 80 140 18900 0.33 | 2.86 1.02 2.05 20.56 60.69 119.5 192.2 256.0 0.6 42.1 18.5 12.6 26.2 2.78 0.630 0.03 80 3.0 1150 20 3.10 80 30 85600 0.47 | 1.2 1.75 3.5 3.623 11.38 63.91 158.6 202.0 2.0 60.2 21.5 10.6 5.7 4.17 0.950 0.25 40 4.74 1200 20 4.89 60 16 145200 1.45 | 1.1 1.62 4.5 5.231 12.56 70.62 182.3 210.5 1.3 65.0 23.5 7.0 3.2 2.50 0.800 8.10 100 5.0 1250 20 5.10 80 10 221500 1.15 |
From above narration as can be seen, flowed cohesion tantalum powder, niobium powder with the inventive method manufacturing have the spheric granules of being similar to, suitable apparent density is arranged, compared with prior art, the metal dust particle diameter of making according to the inventive method distributes more concentrated, less meal (+80 order) and less-32 5 order attritive powders are arranged, mobile better, higher briquet intensity is arranged.Use the pore-size distribution of the tantalum powder sintering body that the pore-size distribution of the sintered body of the tantalum powder sintering that makes according to the inventive method makes than existing method more concentrated, 0.2 the hole of～0.6 μ m is more, minute aperture less than 0.2 μ m is less, hole greater than 1.0 μ m is also less, help being covered electrolyte and cathode material, and useful to the ESR value that reduces electrolytic capacitor.The tantalum that obtains with the inventive method, the electrolytic capacitor anode of niobium powder manufacturing have high specific volume and low leakage current.
The specification of the present invention and the embodiment that are disclosed in herein are exemplary illustrated, and obviously, for a person skilled in the art, the present invention also has other embodiments, and essential scope of the present invention and spirit are determined by claims.
Claims (41)
1. the method for nodularization granulation cohesion metal dust may further comprise the steps:
(a) metal dust is smashed form in diameter D50 less than the fine metal dust of 50 μ m;
(b) the broken fine metal dust that will contain volatile liquid is a granulated into wet granular;
(c), remove volatile liquid and manufacture the particle diameter that increased density less than 1000 microns free-pouring pre-flocculated particle with the static oven dry of wet granular;
(d) above-mentioned free flowing granule is heat-treated;
(e) the heat treatment powder that sieves obtains flowable cohesion metal dust.
2. according to the process of claim 1 wherein that metal dust is the metal dust that comprises tantalum or niobium.
3. according to the process of claim 1 wherein in step (a), with metal dust smash form in diameter D50 less than the fine metal dust of 30 μ m.
4. according to the process of claim 1 wherein in step (b), adopt comminutor to be a granulated into wet granular.
5. according to the process of claim 1 wherein in step (c),, remove volatile liquid and manufacture the particle diameter that increased density less than 500 microns free-pouring pre-flocculated particle with the static oven dry of wet granular.
6. according to each method in the claim 1～5, the liquid in the wherein said step (b) is the deionized water or the aqueous solution.
7. according to each method in the claim 1～5, the amount of the liquid that powder contains in the wherein said step (b) is 2%～50% of a powder weight.
8. according to the method for claim 7, the amount of the liquid that powder contains in the wherein said step (b) is 5%～40% of a powder weight.
9. according to each method in the claim 1～5,50～200 ℃ of oven dry at least 16 hours and finishing in vacuum drying chamber of the drying of the wet granular of the granulation in the wherein said step (c).
10. according to each method in the claim 1～5, the ratio of the apparent density of the former powder before the apparent density of wherein said pre-flocculated particle and the granulation is greater than 1.
11. according to the method for claim 10, the ratio of wherein said apparent density is greater than 1～4.
12. according to the method for claim 10, the ratio of wherein said apparent density is 1.5～2.5.
13. according to each method in the claim 1～5, wherein said step (d) comprises metal dust 850～1700 ℃ of vacuum heat of 20～60 minutes of insulation down.
14. according to the method for claim 13, wherein said step (d) comprises metal dust 900～1400 ℃ of vacuum heat that are incubated 20-60 minute down.
15. comprising, a flowable cohesion tantalum powder that obtains according to each method in the claim 1～14, described cohesion tantalum powder be similar to spherical flocculated particle.
16. according to the cohesion tantalum powder of claim 15, the flowing velocity that described tantalum powder has is at least 2.0g/sec.
17. according to the cohesion tantalum powder of claim 16, wherein said flowing velocity is 4～6g/sec.
18. according to the cohesion tantalum powder of claim 15, described tantalum powder has the above Fei Shi average grain diameter of 1.0 μ m.
19. according to the cohesion tantalum powder of claim 15, described tantalum powder contains a kind of element in O, N, P, B, the Si group at least.
20. according to the cohesion tantalum powder of claim 19, described tantalum powder comprises at least a in the following composition: 0.12%～3% oxygen and 0.005%～10% nitrogen.
21. according to the cohesion tantalum powder of claim 15, the BET specific area that described tantalum powder has is 0.2～6.0m
2/ g.
22. according to the cohesion tantalum powder of claim 21, the BET specific area that described tantalum powder has is 0.8～3.5m
2/ g.
23. according to the cohesion tantalum powder of claim 15, the apparent density that described tantalum powder has is 1.2～5.5g/cm
3
24. according to the cohesion tantalum powder of claim 23, the apparent density that described tantalum powder has is 1.5～2.0g/cm
3
25. according to the cohesion tantalum powder of claim 15, described tantalum powder is to comprise powder granular and/or the sheet primary partical.
26. comprising, a cohesion niobium powder that obtains according to each method in the claim 1～14, described cohesion niobium powder be similar to spherical flocculated particle.
27. according to the cohesion niobium powder of claim 26, the flowing velocity that described cohesion niobium powder has is at least 1.0g/sec.
28. according to the cohesion niobium powder of claim 27, the flowing velocity that described cohesion niobium powder has is at least 2.5～4g/sec.
29. according to the cohesion niobium powder of claim 26, described cohesion niobium powder has the above Fei Shi average grain diameter of 1.0 μ m.
30. according to the cohesion niobium powder of claim 26, described cohesion niobium powder contains a kind of element in O, N, P, B, the Si group at least.
31. according to the cohesion niobium powder of claim 30, described cohesion niobium powder comprises at least a in the following composition: the oxygen of 0.3wt%～12wt% and be the nitrogen of 0.01wt%～10wt%.
32. according to the cohesion niobium powder of claim 26, the BET specific area that described niobium powder has is 0.5～8.0m
2/ g.
33. according to the cohesion niobium powder of claim 32, the BET specific area that described niobium powder has is 1.0～4.5m
2/ g.
34. according to the cohesion niobium powder of claim 26, the apparent density that described niobium powder has is 0.7～2.5g/cm
3
35. according to the cohesion niobium powder of claim 34, the apparent density that described niobium powder has is 1.0～1.6g/cm
3
36. according to the cohesion niobium powder of claim 26, described niobium powder is to comprise powder granular and/or the sheet primary partical.
37. the method for tantalum and/or niobium metal powders is condensed in a nodularization granulation, may further comprise the steps:
(a) tantalum and/or niobium metal powders are smashed the fine metal dust of middle diameter D50 less than 50 μ m;
(b) dry resulting fine metal dust;
(c) mix with broken refining metallic powder with volatile liquid, granulation manufactures wet particle;
(d), remove volatile liquid and manufacture the free-pouring pre-flocculated particle that has increased density less than 1000 μ m with the wet static oven dry of particle;
(e) above-mentioned pre-flocculated particle is heat-treated;
(f) metal dust that sieves and obtain condensing.
38., wherein in step (a), tantalum and/or niobium metal powders are smashed the fine metal dust of middle diameter D50 less than 30 μ m according to the method for claim 37.
39., wherein in step (d),, remove volatile liquid and manufacture the free-pouring pre-flocculated particle that has increased density less than 500 μ m with the wet static oven dry of particle according to the method for claim 37;
40. one kind by the capacitor anode of making according to each described tantalum powder among the claim 15-25, wherein the specific capacitance of this capacitor is 5000～250000 μ FV/g.
41. one kind by the capacitor anode of making according to each described niobium powder among the claim 26-36, wherein the specific capacitance of this capacitor is 10000～300000 μ FV/g.
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| WO2006/000184 | 2006-01-27 | ||
| CNB2006100909132A CN100339172C (en) | 2005-09-29 | 2006-06-30 | Method for spheroidizing and pelletizing to coagulate metal powder, metal powder and electrolytic capacitor anode |
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|---|---|---|---|---|
| CN102806345B (en) * | 2012-04-19 | 2014-07-09 | 潘伦桃 | Device for granulating tantalum powder and method for manufacturing coagulated tantalum powder through granulation |
| CN102768906B (en) * | 2012-08-09 | 2015-10-21 | 中国振华（集团）新云电子元器件有限责任公司 | In a kind of thermal domain environment, the mixed powder of mixing makes the method for anode block of tantalum capacitor |
| WO2015096048A1 (en) * | 2013-12-25 | 2015-07-02 | 宁夏东方钽业股份有限公司 | Capacitor grade high specific volume tantalum powder improving electrical performance and preparation method therefor |
| CN104858436B (en) * | 2014-02-21 | 2018-01-16 | 宁夏东方钽业股份有限公司 | The preparation method of highly reliable Fabrication of High Specific Capacitance electrolytic capacitor tantalum powder |
| CN103934452B (en) * | 2014-05-12 | 2016-07-06 | 宁夏东方钽业股份有限公司 | A kind of dough method of superelevation specific volume tantalum powder and the tantalum powder prepared by the method |
| CN104841929B (en) * | 2015-06-03 | 2019-10-25 | 宁夏东方钽业股份有限公司 | A kind of fine niobium powder and its manufacturing method |
| KR102503996B1 (en) | 2018-03-05 | 2023-03-02 | 글로벌 어드밴스드 메탈스 유에스에이, 아이엔씨. | Spherical tantalum powder, products containing the same, and methods for producing the same |
| CN115570127B (en) * | 2022-10-11 | 2023-07-21 | 江门富祥电子材料有限公司 | Preparation method of tantalum powder |
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